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CN112537779A - Phosphorus modified ZSM-5 molecular sieve and preparation method thereof - Google Patents

Phosphorus modified ZSM-5 molecular sieve and preparation method thereof Download PDF

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CN112537779A
CN112537779A CN202010656386.7A CN202010656386A CN112537779A CN 112537779 A CN112537779 A CN 112537779A CN 202010656386 A CN202010656386 A CN 202010656386A CN 112537779 A CN112537779 A CN 112537779A
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molecular sieve
phosphorus
zsm
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王丽
陈强
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Shanxi Tengmao Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38Type ZSM-5
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026After-treatment

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Abstract

The invention provides a modified ZSM-5 molecular sieve and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and pulping the ZSM-5 molecular sieve, the phosphorus-containing cationic compound and deionized water, heating to 60-90 ℃, continuously stirring for reaction for 0.5-3 hours, then filtering, drying, and roasting at 400-700 ℃ for 1-4 hours to obtain the phosphorus-modified ZSM-5 molecular sieve. The modification method provided by the invention can obtain the phosphorus modified ZSM-5 molecular sieve with high crystallinity and high cracking activity, and has the characteristics of simple process and no phosphorus loss.

Description

Phosphorus modified ZSM-5 molecular sieve and preparation method thereof
Technical Field
The invention relates to a phosphorus modified ZSM-5 molecular sieve and a preparation method thereof, in particular to a phosphorus modified ZSM-5 molecular sieve used for catalytic cracking reaction and a preparation method thereof.
Background
Propylene is one of the most important organic chemicals, the largest use of which is the production of polypropylene, accounting for about 52%, and secondly the production of acrylonitrile 12%, propylene oxide 7%, cumene 7%, isopropanol 4%, carbonyl alcohol 9% and others 9%. With the development of national economy, the demand for propylene is increasing dramatically. In recent years, the demand for propylene has been increasing more than that for ethylene. Naphtha cracking coproduces ethylene and propylene, typically in a propylene to ethylene ratio of 6.5:1, with the shortfall being largely made up by the refinery catalytic cracking (FCC) unit.
The FCC device takes heavy oil as raw material, the reaction operation condition is harsh, and the high yield propylene FCC catalyst is required to have good thermal stability, hydrothermal stability, mechanical strength and heavy metal pollution resistance. Other requirements include moderate rare earth element content, high acid strength, proper acid density, low hydrogen transfer activity and high selectivity to propylene. The molecular sieve with high silicon-aluminum ratio has high acid strength and is beneficial to generating propylene. The conventional FCC unit approach to light olefin production is to select the appropriate catalyst or use an adjunct. Wherein, the adoption of the auxiliary agent containing the ZSM-5 molecular sieve is the most effective method for improving the yield of the light olefin of the catalytic cracking unit at present. At present, ZSM-5 molecular sieve is mostly needed to be used as an active component for the catalyst for catalytic cracking and propylene yield increase. Therefore, in order to improve the hydrothermal stability and cracking reaction activity of the ZSM-5 molecular sieve, the ZSM-5 molecular sieve needs to be modified, and modification by using phosphorus is currently the most common modification method.
The existing ZSM-5 phosphorus modification technology mainly comprises two modes of in-situ synthesis and modification after synthesis. The in-situ synthesis method is characterized in that a phosphorus-containing compound is introduced into a synthesis system of the ZSM-5 molecular sieve in situ, and introduced phosphorus elements enter a framework structure of the molecular sieve in an isomorphous substitution mode, so that the phosphorus-modified ZSM-5 molecular sieve is prepared. For example, CN106315615A discloses a synthesis method of a phosphorus-containing ZSM-5 molecular sieve, which comprises the following steps: (1) mixing quaternary ammonium hydroxide, tetrabutyl phosphorus hydroxide and an aluminum source, treating the mixture in a closed reaction kettle at 50-190 ℃ for 0.1-5 hours, and cooling to obtain an intermediate product, wherein the aluminum source is an aluminum source without alkali metal ions; (2) uniformly mixing the intermediate product obtained in the step (1), a silicon source and water to obtain a mixture; (3) and (3) placing the mixture obtained in the step (2) in a closed reaction kettle for hydrothermal crystallization and recovering the product. Generally, the in-situ synthesis method has complicated process and harsh reaction conditions, and is not beneficial to large-scale production operation; the modification method after synthesis is an ion exchange or impregnation method, and the formed ZSM-5 molecular sieve is subjected to post-treatment by using a phosphorus-containing solution so as to prepare the phosphorus-modified ZSM-5 molecular sieve. Compared with the in-situ synthesis method, the post-synthesis modification method is relatively simple to operate and easy to produce.
Currently, the post-synthesis modification method generally adopts conventional phosphorus-containing inorganic compounds such as phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the like as phosphorus sources (Korean-Tomin, Chenyanhong, Shanhong red and the like. modification research progress of catalytic cracking propylene-productive catalyst ZSM-5 molecular sieves, petrochemical technology and application 2015, (5): 446). However, in these phosphorus-containing compounds, phosphorus is in an anionic group, and the framework structure of the ZSM-5 molecular sieve has a strong negative charge, and a strong charge repulsion exists between the phosphorus and the ZSM-5 molecular sieve, which is not favorable for the combination of the modified phosphorus and the ZSM-5 molecular sieve, thereby greatly limiting the phosphorus modification effect. Therefore, researchers have adopted tetraethoxyphosphine oxide as a phosphorus source and prepared phosphorus modified ZSM-5 molecular sieves (Tyron, Schering, He Ming Yuan, etc.. catalytic Proc., 2017, 38(1): 48-57) by a modification method after synthesis. However, the tetraethoxy phosphorus hydroxide used in the method is strong in basicity, and the framework structure of the molecular sieve is damaged while the ZSM-5 molecular sieve is subjected to phosphorus modification, so that the crystallinity of the modified molecular sieve is reduced.
Disclosure of Invention
In view of the above problems, the present invention provides a phosphorus-modified ZSM-5 molecular sieve and a preparation method thereof, which can simultaneously solve the above problems of charge repulsion between the conventional inorganic phosphorus source and the framework structure of the molecular sieve and the structural damage of the framework structure of the molecular sieve, and the preparation method comprises the following steps:
mixing and pulping a ZSM-5 molecular sieve, a phosphorus-containing cation compound and deionized water, heating to 60-90 ℃, continuously stirring for reaction for 0.5-3 hours, then filtering, drying, and roasting at 400-700 ℃ for 1-4 hours to obtain the phosphorus-modified ZSM-5 molecular sieve.
The ZSM-5 molecular sieve in the preparation method provided by the invention can be one or more of ZSM-5 molecular sieves with different silica-alumina ratios, and also can be one or more of ZSM-5 molecular sieves modified by rare earth ions or other metal cations.
The phosphorus-containing cationic compound in the preparation method provided by the invention can be one or more of tetrakis hydroxymethyl phosphonium chloride, tetrakis hydroxyethyl phosphonium chloride, tetrakis hydroxymethyl phosphonium sulfate and tetrakis hydroxyethyl phosphonium sulfate.
The weight ratio of materials used in the preparation method provided by the invention is ZSM-5 molecular sieve (dry basis): cationic compound containing phosphorus (according to P)2O5Meter): deionized water 1: 0.005-0.05: 2 to 8.
The drying process described in the preparation process provided by the present invention is a method well known to those skilled in the art.
The invention provides a phosphorus modified ZSM-5 molecular sieve and a preparation method thereof, wherein the preparation method takes a phosphorus-containing cationic compound as a phosphorus source and prepares the phosphorus modified ZSM-5 molecular sieve by a modification mode after synthesis. Compared with the existing phosphorus modified ZSM-5 molecular sieve preparation patent technology, the method has the following remarkable advantages: (1) the phosphorus element in the phosphorus-containing cationic compound used in the method is positioned in the cationic group, the ZSM-5 molecular sieve has a skeleton structure with negative charges, and a strong positive and negative charge attraction effect exists between the phosphorus element and the ZSM-5 molecular sieve, so that the modified phosphorus element and the ZSM-5 molecular sieve can be combined very favorably, and the phosphorus modification effect can be more fully exerted; (2) the aqueous solution of the phosphorus-containing cationic compound used in the method is close to neutral, so that the damage of acid dealumination or alkali desilication to the structure of the ZSM-5 molecular sieve skeleton can be avoided, and the crystallinity of the ZSM-5 molecular sieve is not negatively influenced. (3) As the modified phosphorus element and the ZSM-5 molecular sieve have stronger positive and negative charge attraction, the method can carry out filtering operation without loss of the phosphorus element, thereby greatly reducing the energy consumption and time of the subsequent drying process and being very beneficial to large-scale production.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
(1) Evaluation of cracking reactivity (microreflection activity) of molecular sieve sample
The molecular sieve sample is aged for 10 hours at 800 ℃ under the condition of 100% water vapor after being pressed and sieved, and then the micro-inverse activity of the sample is evaluated on a small catalytic cracking device. The reaction raw oil is Hongkong light diesel oil, the reaction temperature is 460 ℃, the reaction time is 70 seconds, the catalyst loading is 5.0 g, and the catalyst-oil weight ratio is 3.3.
(2) Crystallinity analysis of molecular sieve samples
The crystallinity of the molecular sieve sample was analyzed on an x-ray diffractometer model D/max-2200PC manufactured by Rigaku corporation, Japan.
(3) Analysis of phosphorus content of molecular sieve sample
Molecular sieve sample phosphorus element (P)2O5) The content analysis was carried out on a ZSX Primus type fluorescence spectrometer from Rigaku corporation.
(4) Properties of the raw materials
ZSM-5 molecular Sieve (SiO)2/Al2O333, 266, 487), shanxi teng mao science and technology limited, a qualified industrial product;
concentrated phosphoric acid (85 wt%), ammonium phosphate, ammonium dihydrogen phosphate, tetrakis (hydroxymethyl) phosphonium chloride (85 wt%) solution, tetrakis (hydroxymethyl) phosphonium sulfate (75 wt%) solution, commercial reagent (national drug group), analytically pure.
Tetraethylphosphine oxide (40 wt% solution), Sigma-Aldrich, analytical grade.
Example 1
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
480 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O333), 7.57 g of tetrakis (hydroxymethyl) phosphonium chloride and 1200 g of deionized water, stirring, heating to 60 ℃, continuously stirring for reaction for 3 hours, filtering, drying, and roasting at 500 ℃ for 3 hours to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-S1.
Example 2
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
535 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O333), 3.05 g of tetrakis (hydroxymethyl) phosphonium sulfate and 2140 g of deionized water, beating, heating to 70 ℃, continuously stirring for reaction for 2 hours, filtering, drying, and roasting at 400 ℃ for 4 hours to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-S2.
Example 3
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
615 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O333), 29.2 g of tetrakis (hydroxymethyl) phosphonium chloride, 35.3 g of tetrakis (hydroxymethyl) phosphonium sulfate and 4920 g of deionized water, beating, heating to 90 ℃, continuously stirring for reaction for 0.5 hour, filtering, drying, and roasting at 700 ℃ for 1 hour to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-S3.
Example 4
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
490 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3266 percent), 74.7 grams of tetrakis hydroxymethyl phosphonium sulfate and 3920 grams of deionized water, beating, heating to 85 ℃, continuously stirring for reaction for 1 hour, then filtering, drying, and roasting at 550 ℃ for 2.5 hours to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-S4.
Example 5
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
560 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3266 percent), 8.83 grams of tetrakis hydroxymethyl phosphonium chloride, 10.7 grams of tetrakis hydroxymethyl phosphonium sulfate and 1400 grams of deionized water are mixed and pulped, the temperature is raised to 75 ℃, the reaction is continuously stirred for 1.5 hours, then the mixture is filtered and dried, and the mixture is roasted for 1 hour at the temperature of 650 ℃, thus obtaining the phosphorus modified ZSM-5 molecular sieve PZSM-S5.
Example 6
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
605 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3266 percent), 38.2 grams of tetrakis hydroxymethyl phosphonium chloride and 2420 grams of deionized water, beating, heating to 65 ℃, continuously stirring for reaction for 2.5 hours, then filtering, drying, and roasting at 450 ℃ for 3 hours to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-S6.
Example 7
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
675 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3487), 26.5 g of tetrakis (hydroxymethyl) phosphonium chloride, 32.03 g of tetrakis (hydroxymethyl) phosphonium sulfate and 2700 g of deionized water are mixed and pulped, the temperature is raised to 70 ℃, the mixture is continuously stirred and reacted for 2 hours, then the mixture is filtered and dried, and the mixture is roasted for 2 hours at the temperature of 550 ℃, so that the phosphorus modified ZSM-5 molecular sieve PZSM-S7 is obtained.
Example 8
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
460 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3=487)Mixing 11.7 g of tetramethylolphosphonium chloride and 3680 g of deionized water, pulping, heating to 80 ℃, continuously stirring for reaction for 1.5 hours, then filtering, drying, and roasting at 600 ℃ for 1.5 hours to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-S8.
Example 9
The method of the invention is used for preparing the phosphorus modified ZSM-5 molecular sieve.
585 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3487), 78 g of tetrakis (hydroxymethyl) phosphonium sulfate and 1463 g of deionized water are mixed and pulped, the temperature is raised to 60 ℃, the mixture is continuously stirred and reacted for 3 hours, then the mixture is filtered and dried, and the mixture is roasted for 2.5 hours at the temperature of 500 ℃, so that the phosphorus modified ZSM-5 molecular sieve PZSM-S9 is obtained.
Comparative example 1
The phosphorus modified ZSM-5 molecular sieve is prepared by taking concentrated phosphoric acid as a phosphorus source.
535 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O333), 12.8 g of concentrated phosphoric acid and 2140 g of deionized water, beating, heating to 70 ℃, continuously stirring for reaction for 2 hours, then filtering, drying, and roasting at 400 ℃ for 4 hours to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-D1.
Comparative example 2
And preparing the phosphorus modified ZSM-5 molecular sieve by using ammonium phosphate as a phosphorus source.
605 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3266 percent), 25.4 grams of ammonium phosphate and 2420 grams of deionized water, beating, heating to 65 ℃, continuously stirring for reaction for 2.5 hours, then filtering, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-D2.
Comparative example 3
And preparing the phosphorus modified ZSM-5 molecular sieve by using ammonium dihydrogen phosphate as a phosphorus source.
675 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3487), 26.9 g of ammonium dihydrogen phosphate and 2700 g of deionized water are mixed and pulped, the temperature is raised to 70 ℃, the mixture is continuously stirred and reacts for 2 hours, then the mixture is filtered and dried, and the mixture is roasted for 2 hours at the temperature of 550 ℃, so that the phosphorus modified ZSM-5 molecular sieve P is obtainedZSM-D3。
Comparative example 4
The phosphorus modified ZSM-5 molecular sieve is prepared by taking tetraethyl phosphine oxide as a phosphorus source.
615 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O333), 106.7 g of tetraethyl phosphine oxide and 4920 g of deionized water, heating to 90 ℃, continuously stirring for reaction for 0.5 hour, filtering, drying, and roasting at 700 ℃ for 1 hour to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-D4.
Comparative example 5
The phosphorus modified ZSM-5 molecular sieve is prepared by taking tetraethyl phosphine oxide as a phosphorus source.
490 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3266 percent), 113.1 grams of tetraethyl phosphine oxide and 3920 grams of deionized water, beating, heating to 85 ℃, continuously stirring for reaction for 1 hour, then filtering, drying, and roasting for 2.5 hours at the temperature of 550 ℃ to obtain the phosphorus modified ZSM-5 molecular sieve PZSM-D5.
Comparative example 6
The phosphorus modified ZSM-5 molecular sieve is prepared by taking tetraethyl phosphine oxide as a phosphorus source.
460 g of ZSM-5 molecular sieve (dry basis, SiO)2/Al2O3487), 21.3 g of tetraethyl phosphine oxide and 3680 g of deionized water, stirring, heating to 80 ℃, continuously stirring for reaction for 1.5 hours, filtering, drying, and roasting at 600 ℃ for 1.5 hours to obtain the phosphorus-modified ZSM-5 molecular sieve PZSM-D6.
TABLE 1 physicochemical Properties of different molecular Sieve samples
Figure BDA0002576919020000061
Table 1 lists the physicochemical property data of different molecular sieve samples. It can be seen that the same P was used for the preparation system2O5In the case of the molecular sieve weight ratio, the method of the present invention produces a phosphorus modified ZSM-5 sample (PZSM-D-1, PZSM-D2, PZSM-D3) as compared to the comparative examples prepared using conventional inorganic phosphorus sources (PZSM-D1, PZSM-D2, PZSM-D3)S2, PZSM-S6 and PZSM-S7) phosphorus element content measured value has no obvious difference with a theoretical value, while the comparative sample phosphorus element content measured value has a larger difference with the theoretical value, which is mainly benefited by the strong charge attraction effect between the phosphorus cation compound used in the method and the ZSM-5 molecular sieve, and the phosphorus element loss caused by the filtering process can be effectively avoided; in addition, although the comparative samples (PZSM-D4, PZSM-D5 and PZSM-D6) prepared by using tetraethyl phosphine oxide as a phosphorus source have no problem of loss of modified phosphorus element, the crystallinity of the prepared phosphorus-modified ZSM-5 molecular sieve is obviously reduced compared with that of the parent ZSM-5 molecular sieve due to the damage of strong basicity of the tetraethyl phosphine hydroxide to the molecular sieve structure, and the crystallinity of the corresponding modified molecular sieve samples (PZSM-S3, PZSM-S4 and PZSM-S8) prepared by the method is not obviously reduced.
TABLE 2 microreactivity data for different molecular sieve samples
Figure BDA0002576919020000071
The microreactivity data for different molecular sieve samples are given in table 2. Compared with an unmodified ZSM-5 molecular sieve parent, the phosphorus modified ZSM-5 molecular sieve sample prepared by the method has the advantages that the micro-inverse activity is generally improved by more than 7-13 percent, the activity increase amplitude is obviously higher than that of a corresponding comparative sample, and the method has a good modification effect.

Claims (4)

1. The modified ZSM-5 molecular sieve is characterized by comprising the following steps: mixing and pulping a ZSM-5 molecular sieve, a phosphorus-containing cation compound and deionized water, heating to 60-90 ℃, continuously stirring for reaction for 0.5-3 hours, then filtering, drying, and roasting at 400-700 ℃ for 1-4 hours to obtain the modified ZSM-5 molecular sieve.
2. The phosphorus-modified ZSM-5 molecular sieve of claim 1, wherein the ZSM-5 molecular sieve in the preparation method may be one or more of ZSM-5 molecular sieves with different silica-alumina ratios, or one or more of ZSM-5 molecular sieves modified by rare earth ions or other metal cations.
3. The phosphorus-modified ZSM-5 molecular sieve of claim 1, wherein the phosphorus-containing cationic compound in the preparation method is one or more of tetrakis hydroxymethyl phosphonium chloride, tetrakis hydroxyethyl phosphonium chloride, tetrakis hydroxymethyl phosphonium sulfate and tetrakis hydroxyethyl phosphonium sulfate.
4. The phosphorus-modified ZSM-5 molecular sieve of claim 1, wherein the preparation method uses a weight ratio of materials of ZSM-5 molecular sieve (dry basis): cationic compound containing phosphorus (according to P)2O5Meter): deionized water 1: 0.005-0.05: 2 to 8.
CN202010656386.7A 2020-07-09 2020-07-09 Phosphorus modified ZSM-5 molecular sieve and preparation method thereof Pending CN112537779A (en)

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EP2039427A1 (en) * 2007-09-12 2009-03-25 Total Petrochemicals Research Feluy Cracking of olefins on phosphorus modified molecular sieves
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113264538A (en) * 2021-05-29 2021-08-17 山西腾茂科技股份有限公司 Preparation method and application of molecular sieve adsorbent based on LiNaKLSX

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Application publication date: 20210323